Method of incorporating metal complexes in a base oil



METHOD OF INCORPORATING METAL. COMPLEXES IN A BASE OIL Filed July 7, 1958 United Sites 3,055,829 METHUD OF INCORPORATHNG METAL CGMPLEXES IN A BASE OlL Morris A. Wiley and Herman l). Kluge, Fishkill, N.Y., assignors to Texaco Inc., a corporation of Delaware Filed July 7, 1958, Ser. No. 747,089 13 Claims. (Cl. 252-18) This invention relates to a method of incorporating metal complexes in a base oil to form concentrates useful as additives for lubricating and fuel preparations.

In copending, coassigned application Serial No. 645,667, filed March 13, 1957, by Herman D. Kluge, Morris A. Wiley and Kenneth L. Kreuz, now abandoned, an excellent method of incorporating alkali and alkaline earth metal compounds in oils is disclosed, wherein a metal base, a dispersant and a lubricating oil are heated together at a temperature of from 250 to 450 F. with oxygen blowing for a number of hours and then heated to a temperature at least 50 F. higher than the iirst heating with continued oxygen blowing for several more hours to obtain the desired product. The present invention is similarly concerned with the incorporation of metal compounds in oils to form complexes having superior additive properties in hydrocarbon and synthetic fluid compositions.

The process of this invention incorporates substantial amounts of dispersed metal compounds in ian oil at a relatively low cost per unit of added metal and permits excellent control of the amount of metal compound finally present in the product.

The method of this invention for `forming metal complexes comprises heating a metal carboxylate in the presence of excess basic reacting inorganic metal compound and a heat stable dispersant in a lubricating oil to a 3 temperature between 400 and 850 F., effecting conversion of a substantial portion of said metal carboxylate to metal base during said heating treatment, and cooling to form a concentrate containing the dispersant, met-al carboxylate and metal base. Generally, a carboxylic acid or material consisting essentially thereof is heated in the presence of excess basic reacting metal compound to form a metal carboxylate containing product which product is then heated to a temperature from 400 to 850 F. in the presence of a dispersant in a lubricating oil. The conversion of a substantial portion of metal carboxylate to metal base within this temperature range is most effectively carried out in an inert atmosphere.

The dispersants used in the method of this invention are metal salts of organic acids having high solubility in lubricating oils and which must be heat stable at temperatures of at least 400 F. and preferably as high as 850 F. These acids must have a minimum solubility of parts per 100 parts of oil. Examples of the dispersant include normal, basic, and superbased oil soluble petroleum (mahogany) sulfonates. Synthetic sulfonates such as alkyl aryl sulfonates lderived from alkylated benzene or naphthalene may also be used. Other useful dispersants include metal alkyl phenolates or sulfurized alkyl phenolates, the alkyl `groups in each case desirably having at least 8 carbon atoms, advantageously 8 to 60; salts of alkyl phenol-formaldehyde condensation products; salts of hexamethylene tetramine-alkyl phenol condensation products; naphthenates and naphthenic acids; and the metal salts of olen-phosphorus sulfide reaction products.

The dispersant per se is added in the initial stage of the process of the invention or it is added just prior to the elevated temperature conversion of the carboxylate to carbonate (thermal decarboxylation step), particularly if the carboxylate is formed in situ. In the preferred form of the invention, the dispersant is formed in situ. For example, a sulfonic acid, naphthenic acid, olefn-P2S5 product, alkyl phenol or derivative thereof is heated in the presence of the basic reacting inorganic metal compound (metal base) to form the salt at the same time the metal 5 carboxylate is formed in the process of the invention.

The amount of the dispersant which is beneficial in the process of the invention is dependent on the amount of metal compounds to be dispersed. Generally, the amount of dispersant 1used is from '1.0 to 40.0 (mol) percent and preferably from 4.0 to 20.0 percent of `the stoichiometric quantity of metal employed in the process. Of course, a greater amount of dispersant than specified may be used, however, generally speaking, higher amounts do not increase the amount of metal incorporated in the lubricating base oil.

One of the best dispersing agents is an oil soluble metal petroleum sulfonate made from a sulfonic acid having a molecular weight `of about 350-450; however, synthetic sulfonates derived from alkylated benzene or naphthalene are also excellent. Another preferred dispersant is the metal salt of a polyisobutylene (average molecular weight 700 to 800) -P2S5 reaction product.

The basic reacting inorganic metal compounds which are useful include the oxides, hydroxides and carbonates of alkali and alkaline earth metals, magnesium, zinc, cadmium, tin, lead and manganese. The preferred metal compounds based on their comparative usefulness inthe process of the invention are the oxides and hydroxides of barium, calcium, magnesium, and lithium.

The amount of the metal compound which is effectively employed in the process of this invention is dependent on the amount of acid material employed in the initial step of the process. The metal compound should be present in an amount in excess of the stoichiometric quantity theoretically required for neutralization and saponication of the carboxylic acid, acid derivatives or other acidic materials present. Generally, amounts within the range of from 20 to 400 percent in excess are applicable. bly, the metal compound should be present in the amount of about 50 to 200 (wt.) percent in excess of the stoichiometric quantity theoretically required to completely saponify the carboxylic acid, its derivatives, or other acidic material present. When excess amounts, for example from 200 to 400 percent of basic metal compound are used above that theoretically required to completely saponify the carboxylic acid or its derivatives, greater amounts of dispersant material should be employed as previously stated.

Water is desirably employed in the reaction to promote saponiiication and reactiveness of the metal base compounds. Generally, about il.0 to 30 (wt.) percent of water based on the charge materials were found helpful and preferably 5.0 to 10l percent of water was used.` The carboxylic acids used in the process of this inven-" tion include Ialiphatic carboxylic acids, for example, formic, acetic, propionic, acrylic, butyric, valerie, sorbic, capric, caproleic, lauric, myristoleic, palmitic, oleic, stearic, vaccenic, linoleic, linolenic, behenic, cerotic, montanic, melissic, naphthenic and chaulmoogric acid. Carboxylic acids containing other functional groups are useful. These include, for example,hydroxy carboxylic acids such as lactic, 2-hydroxycaprylic, Z-hydroxylauric, 16-hydroxypalmitic, 12-hydroxystearic, 11,12-dihydroxystearic, lanoceric, and ricinoleic acid. 'Ilu's group also includes lieto-carboxylic acids such as pyruvic, acetoacetic, 4keto caproic, Z-ketolauric, 9-ketostearic yand lO-ketobehenic acid. Dicarboxylic acids are lalso used;rexamples of such acids are malonic, maleic, succinic, itaconic, adipic, suberic, azalaic, sebacic land eicosanedioic acid. The aromatic and substituted aromatic carboxylic acids are in a like manner useful materials for this invention. Some exam- Preferaples are benzoic, salicylic, alkylsalicylic, tropic, phthalic and divaric acid.

Acidic materials produced by oxidation of organic compounds are other useful materials for this invention and are at times preferred because they are inexpensive and easily obtainable. These products include oxidized mineral oils, acid type wax oxidates, ester type wax oxidates, overhead condensates from oxidation processes, distilled fractions of oxidates, naphtha soluble fractions of oxidates, etc. Not to be omitted from the useful carboxylic acid-containing materials are the naturally occurring fatty materials, such as lard, vegetable oils, animal residues, and glycerides. In some instances, other organic materials such as esters, amides and the like are suitable sources of acid radicals.

Both economic considerations and quality of product dictate a preference for low molecular weight aliphatic carboxylic acids, particularly formic and acetic acids, and for acidic material produced by oxidation of mineral oils, wax, etc., as the carboxylic acid material for use in this invention. The amount of carboxylic acid which is used in the process of this invention is such as to provide a metal complex containing concentrate having dispersed therein from 0.1-15 weight percent of metal carbonate, 1-40 weight percent dispersant, and 0.5-30 weight percent metal carboxylate; the metal being present in the oil in an amount of at least 1.0 weight percent and not exceeding 25 percent. As a practical matter the carboxylic acid usually constitutes from 5 to 50 (wt.) percent of the reaction mixture and preferably to 35 (wt.) percent.

The base oils which are used in the process of this invention include hydrocarbon oils and synthetic uids. Naphthene, paraffin and residual type mineral lubricating oils, and mixtures thereof are normally employed. These oils include those which have been subjected to all types of refining techniques including hydrorening. Synthetic base fluids such as high molecular weight polybutenes are also included.

The saponifcation step of the process of the invention may be made to take place separately in order to form the carboxylate and dispersant in situ at a temperature and time sufficient to cause saponification but insufficient to cause any decarboxylation. The temperature at which saponification of the carboxylic acid takes place by re- -action with the metal base and at which a reaction occurs between the dispersant precursor Kacid and the metal base ranges from about 125 F. to about 250 F. The reaction is Iadvantageously carried out at about 175 to 250 F. and preferably from 180 to 220 F. The time required to-complete the reaction at these temperatures ranges from about 5 minutes to 4 hours. It is frequently desirable to introduce a solvent, such as water or petroleum hydrocarbon, such as heptane, to promote ease of saponiiication.

After saponication of the carboxylic acid is com-V pleted and the dispersant precusor acid has formed its salt, if such is the case, the reactants are subjected to the thermal decomposition step. Assuming the dispersant is not formed in situ the dispersant per se may be added to the mixture just prior to the thermal decomposition or just prior to saponification.

Generally the thermal decomposition step consists of subjecting the saponified material to temperatures ranging from 400 to 850 F. preferably in an inert atmosphere for a time period ranging from about la minute to several hours; for example, 1 minute to l0 hours. The preferred decomposition temperature ranges from about 600 to 700 F. for a time period of from 3 to 15 minutes.

Alternatively, -tlie separate saponification step is dispensed with and the initial reaction mixture is subjected to thermal decomposition immediately. Under such conditions, -saponication and thermal decomposition to form the metal carbonates, take place almost simultaneously. The optimum conditions of time and temperature for the thermal decomposition step are dependent in each case on the stability of the lbase oil and the type of carboxylate selected. Temperatures above about 850 F. should not be used to avoid decomposition of the base oil and of the dispersing agent. Generally speaking, higher temperatures and longer time periods within the prescribed ranges will cause a desirable increase in the amount of dispersed metal compounds in the finished product.

The inert atmosphere preferred during the step of thermal decomposition is normally obtained by blowing nitrogen, argon or other inert gas through the oil-metal cornpound mixture. Air exclusion may also be accomplished by vacuum operation. The rate of blowing of the inert gas through the reaction vessel is sufficient to prevent oxygen or other reacting gas from contacting the compounds in amounts large enough to cause oxidation or unwanted changes therein. Amounts of nitrogen, for example, of the order of l or 2 liters per minute have been blown through a volume of from 0.5 to 5.0 liters of ingredients present during the performance of the process of the invention.

To finish the metal complex containing concentrates of the invention, they are generally filtered to remove excess solids thereafter obtaining clear, filterable and stable complexes.

At times, in order to convert any remaining metal oxide or hydroxide still present in the complex, or dispersed in colloidal form, to a neutral salt the product is carbon dioxide blown at about 15G-450 F., conveniently at Z50-350 F., for about five minutes to four hours. Other acidic gases such as hydrogen sulfide or sulfur dioxide may be employed for blowing to obtain a neutral product.

While the composition of the metal complex containing concentrate produced by the process of this invention may be complicated and of a complex nature, it is believed to generally comprise a base oil as a major component, 0.1-15 weight percent metal carbonate or other metal base, 1-40 weight percent dispersant, and 0.5-30 weight percent metal carboxylate. The metal content of the oil is at least 1 weight percent and not exceeding 25 percent and generally is between 2 and 15 weight percent. At least a major portion of the metal carbonate or metal base is obtained by decomposition of the carboxylic acid salt. Minor amounts of inorganic base, as such, are usually dispersed during the processing.

The metal complex is an excellent detergent additive for hydrocarbon compositions notably lubricants. It is generally incorporated in lubricant composition in amounts wherein the metal compound content is from 0.1 to 5 percent by weight of the total lubricant composition.

Examples of the process of this invention utilizing various reactants and conditions, and setting forth the excellent products formed are given as follows:

EXAMPLE I 1,040 g. of a refined oxidate from a furfural refined, light acid treated, clay contacted and solvent dewaxed parafn base wax distillate were charged to a reaction vessel. The crude oxidate from which this refined material was derived was prepared by the method set forth in copending, coassigned application Serial No. 710,856, filed January 24, 1958, by George B. Kirkwood and John H. Greene. In accordance with this method the refined parainic oil is reacted with air in the presence of a metalliferous oxidation catalyst. The preferred conditions include an air feed rate of 10-25 cu. ft. per lbs. oil per hour, an air velocity of about 0.2-1 ft. per sec., au oxidation initiation temperature of B30-370 F., an oxidation reaction temperature of 260-300 F., a reaction pressure of 50-90 p.s.i.g. and a potassium permanganate catalyst in an amount of 0.4 to 1.2 percent by weight based on the charge oil. Oxidation is continued to a Neutralization No. of between 55 and 70.

The refined oxidate was obtained by washing crude oxidate with .a 40 percent solution of H280.,t in water at about 140 F. and then with water at about 150 F. The purpose of the sulfuric acid and water washes was t0 remove any metal present as metal naphthenates. These metal naphthenates originate from the transition metal catalyst employed in the preparation of the petroleum oxidate. The oxidate was then dried by nitrogen blowing at 210 F. The refined oxidate had a Saponication No. of 108, a Neut. No. of 58.2 and a calculated combining weight of approximately 520 g. on the basis of the Sap. No

200 g. of .a petroleum sulfonic acid having a Neut. No. of 36.4 in a mineral oil carrier, 347 g. of isoheptane as a solvent for the sulfonic acid concentrate, 1320 g. of a refined naphthene base distillate oil having a gravity API of 18.4 and a viscosity SSU at 100 F. of 1663, 112 g. of powdered calcium oxide and 180 ml. of water were also charged to the reaction vessel. Isoheptane is a petroleum solvent of the approximate boiling range of a mixture of heptanes. It is a useful solvent which can be readily stripped from the reaction mixture by distillation.

The indicated calculated stoichiometric quantities or ratios for each of the reaction components of the mixture were as follows:

Table I Calcium oxide (basis theoretical combining wt.) 4.0 Oxidate (basis Sap No.) 2.0 Sulfonic acid (basis Neut. No.) 0.3

The mixture in the reaction vessel was refluxed at a temperature of 195 F. for two hours with stirring to effect saponification and neutralization after which time the temperature was raised to 650 F. for 5 minutes with nitrogen blowing at a rate of 2 liters per minute. The resulting product was then filtered to produce a clear bright product showing the following test results:

Table II Ca, percent 2.9 CO2, percent 0.95 Neut. No. (alli.) 22.0

It was calculated that this product contained about 2.2 (wt.) percent dispersed calcium carbonate (basis carbon dioxide analysis) and about 1.5 (wt.) percent dispersed lime (basis neutralization number).

EXAMPLE II an ethyl ether solution of the crude oxidate with a 40- percent H2504 solution and then with water at 190 F. to remove metals present from spent oxidation catalyst. The ether was then evaporated on a steam plate. For certain contemplated purposes it would not be necessar or desirable to feline the oxidate as above.

188 g. of a refined naphthene base distillate oil having a gravity API of 18.4 and a viscosity SSU at 100 F. of 2566, 20 g. of the sulfonic acid concentrate and 34 g. isoheptane solvent of Example I, 11.2 g. of powdered calcium oxide and 18 ml. of water were also charged to thereaction vessel.

The stoichiometric quantities for each of the reacting components of the mixture were as follows:

.- ample I were charged to a reaction Vessel.

'I'he contents of the reaction vessel were saponified by reuxing for 1 hour at 195 F. with stirring. The mixture was then blown with nitrogen at the rate of 1 liter per minute while the temperature in the vessel was raised to 550 F. and kept there for 5 minutes; the solvents were distilled during this treatment. The material was then filtered to obtain a clear bright product.

The above procedure was carried out three more times with the naphtheue base oil described in Example I and each time raising the temperature 50 F. for the second heating step with nitrogen blowing. The following table sets forth the test results and calculations on each of the four products:

Table IV Calcu- Calcu- Calcu- Ternp. Ca, CO2, lated, lated lated number Product F. percent percent percent CaCOa, Ca(OH)z, (alk.)

Ca as percent percent CaC Os From the above table it is evident that a-n increase in the temperature from 550 F. to 700 F. during the decomposition period increases the amount of dispersed calcium in the concentrate. Furthermore, an increase in the `amount of calcium present in the form of calcium carbonate is also realized.

EXAMPLE III 56 g. `of lthe base oil described in Example I and 63 g. of the crude oxidate tof lthe parain distillate used in Ex- This oxidate material had a Neu-t. No. tof 69, a Sap. Nc. of 134 and a calculated combining weight yof 418 g. 10 g. of the sulfonic acid concentrate in 17 g. isoheptane of Example I, 5.6 g. of calcium oxide and 9 inl. cf water were also charged to the reaction vessel.

The stoichiometric ratios of these materials were as follows:

Table V Calcium loxide 2.0 Oxidate (basis Sap. No.) 1.5 Sultonic acid (basis Neut. No.) 0.175

The materials in Ithe reaction vessel were first reuxed for 3 hours at 195 Iwith stirring. The resulting mass was then blown with nitrogen :at a rate (of 1.0 liter per minute while heating to 650 F. and while the temperature was kept at 65 0 F. for 5 minutes. rThe product was then cooled 'to 350 F. and blow-11 with `CO2 yfor l hour at the rate of 1.0 liter per minute. 4-It was then filtered lto produce a `black and tarry mass. This was thought to be the result of insufficient basic inorganic met-al compound. Prefenably, the inorganic base material should lbe present at least in the amount of from 50 to 200 percent in excess of that amount required to neutralize an acidic material of the oxidate class.

EXAMPLE IV 207 g. of the base cil described in Example'l, 42 g. of the crude wax oxidate material described in lExample Il, 10 g. cf Ithe sul-fonic acid concentrate in 17 g. isoheptane of Example lI, 11.2 g. cf powdered calcium oxide fand 18 inl. of water were charged :to a reaction vessel.

The materials in the reaction vessel were refluxed for 2 hours Iat 195 F. with stirring to cause saponi-fication. After this the mass was blown with nitrogen at the rate of 1.0 liter per minute while heating to 650 F. The temperature was kept at 65 0 F. for 5 minutes with continued nitrogen blowing. After the 5 minute period the nitrogen blowing was stopped 4and the temperature allowed to drop fto 350 at which point it was kept while the mass was blown `with carbon dioxide at the `nate of 1.0

Table Vl Stoichiometric ratio Ingredients 1st preparation 2nd preparation Calcium oxide Oxidate Su ionic acid The results of tests on `the products of these preparations were as follows:

Table VII Calcium, Percent CO2, Percent Neut. number (alk.)..

It was calculated that 59 percent of the calcium in the second product was in :the form of dispersed calcium carbonate.

A comparison of the stoichiometric quantities of the preparations and the test findings for the two products of Example IV indicate that an overly large stoichiometric quantity of calcium oxide (300 percent in excess of the carboxylic acid containing material) results in a low calcium content in the base oil in this process. On the other hand when the amount of dispersant, or in this case its precursor sul-tonic acid is suiciently increased when such a large excess of calcium oxide is used, a high calcium content in the resul-tant additive is observed. As previously stated, the amount of dispersant used ranges from 1.0 to 40 wit. percent of Ithe stoichiometric quantity of the metal employed. The results in this example prove the desirability of using amounts in the range of 8 lto 20 wt. percent of the stoichiometric `amount of metal when large excesses of the Ibasic inorganic metal compounds are lused. For maximum economy of manufacture it is generally desirable to keep :the natio of dispersing agent as low as practical for the desired metal content.

EXAMPLE V 1535 g. of the base oil of Example I, 260 g. of the oxidate material of Example I, 52 g. of 88 percent formic acid, 100 g. of the `Sulfonic acid concentr-ate in 173 g. isoheptane of Example I, 84 g. of calcium oxide and 135 ml. of water were charged lto a reaction vessel. The stoichiometric quantities employed for the reactants are as follows:

Table VIII Calcium oxide 3.0 Oxidate 0.5 Formic acid 1.0 Sultonic acid 0.177

The results of tests on the product are as follows:

Table IX Calcium, percent 2.6 CO2, percent 2.22

It was calculated that about 78 percent of the calcium present was in the form of dispersed calcium carbonate.

This foregoing example illustrates the usefulness of the low molecular weight fatty acids in the process of this invention.

EXAMPLE VI 84 g. of the base oil of Example I, 31.3 g. of behenic acid (87.3% free fatty acid), 13.3 g. of the Sulfonic acid concentrate in 23 g. isoheptane of Example I, 5.6 g. of Ipowdered calcium oxide and 9 ml. of water were charged to a reaction vessel. The stoichiometric ratio of reactants employed was as follows:

Table X Calcium oxide 2.0 Behenic acid 1.0 Sulfonic acid 0.236

This mixture was saponified by reuxing for 2 hours at F. with stirring. The saponied mixture was then blown with l liter of nitrogen per minute while heating to 650 F. and for 5 minutes at that temperature. A sample was taken and liltered upon cooling to 350 F. an analysis showed that this sample contained 2.79 percent calcium and 0.90 percent CO2. The resultant mass remaining in the reactor was then blown with 0.3 liter of CO2 per minute at 350 F. for 30 minutes and then filtered to produce a clear, light, and bright product showing the following test results:

Table X1 Calcium, percent 2.91 CO2, percent 0.91 Neut. No. 0.28

It was calculated that about 28 percent of the calcium present was in the form of dispersed calcium carbonate.

EXAMPLE VII 176 g. of the base oil of Example I, 56.4 g. of oleic acid, 26.6 g. of the sulfonic acid concentrate in 46 g. isoheptane of Example I, 11.2 g. of calcium oxide, and 18 ml. of water were charged to a reaction Vessel. The stoichiometric ratios of reactants employed were as follows:

Table XII Calcium oxide 2.0 Oleic acid 1.0 Sulfonic acid 0.24

Table XIII Calcium, percent 2.94 CO2, percent .27 Neut. No. (alkaline) 7.21

EXAMPLE VIII 84 g. of the base oil of Example I, 30 g. of 85% pure 12-hydroxy stearic acid derived from hydrogenated castor oil, 13.3 g. of the Sulfonic acid concentrate in 23 g. isoheptane of Example I, 5.6 g. of calcium oxide, and 9 ml. of water were charged to a reaction vessel. The approximate stoichiometric ratios for the reactants were as follows:

Table XIV Calcium 2.0 12-hydroxy stearic acid 1.0 Sulfonic acid 0.24

The ingredients were reuxed for 2 hours at 195 F. -with stirring to cause saponifcation. The saponiiied mass Was then decarboxylated by blowing with 1 liter of nitrogen per minute while heating to 650 F. The mass was heated for minutes at this temperature with continued nitrogen blowing. The product was then filtered to produce a clear, bright fluid showing the following test results:

Table XV Calcium, percent 2.75 CO2, percent 0.56 Neut. No. (alkaline) 11.3

It was calculated that approximately 19 percent of the calcium present was in the form of dispersed calcium carbonate and 15 percent as dispersed calcium hydroxide.

EXAMPLE IX 138 g. of the base oil of Example I, 93.5 g. of alkylsalicylic acid solution in oil, 27 g. of the sulfonic acid concentrate in 46 g. isoheptane7 of 'Example I, 11.2 g. of calcium oxide, and 18 ml. of water were charged to a reaction vessel. The stoichiometric amounts of the reactants are as follows:

` Table XVI Calcium 2.0 Alkylsalicylic acid (basis both carboxyl and hydroxyl functions) 1.0 Sulfonic acid 0.24

The ingredients were refluxed for 4 hours at '195 F. with stirring to cause saponilication. The saponied mass was heated to 650 F. while blowing with 1 liter of nitrogen per minute. The heating at this temperature was maintained for 5 minutes with nitrogen blowing. The product was filtered to obtain a bright liquid showing the following test results:

Table XVII Calcium, percent 1.71 CO2, percent i .40 Neut. No. (alkaline) 20 EXAMPLE X LiOHH2O and 18 ml. of water were charged to a reaction vessel.

The stoichiometric ratios employed for the reactants were as follows:

Table X VIII Lithium hydroxide 4.0 Oxidate 1.25 Sulfonic acid 0.35

These ingredients were stirred for 1 hour at 190 F. Then, while raising and maintaining the temperature to 650 F. for 5 minutes, the reactants were blown with 1 liter of nitrogen per minute. Thereafter the product was filtered to obtain a clear product showing the following test results:

10 Table XIX Lithium, percent 0.64 CO2, percent 0.28 Neut. No. (alkaline) 12.0

It was calculated that about 69 percent of the lithium present was in the form of dispersed lithium carbonate.

EXAMPLE XI g. of the base oil of Example I, 51 g. of the wax oxidate of Example X, 19.8 g. of the sulfonic acid concentrate in 34 g. isoheptane of Example I, 8.0 g. of magnesium oxide, and 18 ml. of water were charged to a reaction vessel. The stoichiometric ratios for the reactants were as follows:

Table XX Magnesium oxide 2.0 Oxidate 1.0 Sulfonic acid 0.18

The ingredients were `stirred for 2 :hours at about 190 F. Then, While heating to 650 F. and maintaining that temperature for 5 minutes, the reacting mass was blown with 1 liter of nitrogen per minute. The product was filtered to produce a bright fluid showing the following test results: v

Table XXI Magnesium, percent 2.34 CO2, percent 0.24

EXAMPLE XII 121 g. of the base oil of Example I, 51 g. of the reiined Oxidate of Example X, 19.8 g. of the sulfonic acid concentrate in 34 g. isoheptane of Example I, 16.3 g. of zinc oxide, and 18 ml. of water were stir-red in a -reaction vessel for 1 hour at 190 F. I'he st-oichiometric ratios for the reactants were as follows:

Table XXII Zinc oxide 4.0 Oxidate 1.25 Sul-fonia acid 0.35

The reactants were then heated to 650 F. and mainr tained `at this temperature while l liter 'of nitrogen per minute was blown through the mass. The product was filtered to obtain a iiuid showing the following test results:

Table XXIII Zn, percent 2.38 CO2, percent 0.039 Neut. No. 4.71

EXAMPLE XIII 121 g. of the base oil of Example 'I, 51 g. Xof the rened wax oxida-te of Example X, 19.8 g. of the sulfonic acid concentrate in 34 g. isoheptane of Example I, 27 g. of tin oxide -and 18 ml. of water were saponilied by reliuxing Ifor 2 hours at 195 F. with stirring. The stoichiometric ratios employed for the reactants were as follows:

Table XXIV Tin `oxide 4.00 Oxidate 1.25 Sulfonic acid 0.35

The mass was lthen blown with 1 liter `of nitrogen per minute as the temperature was raised to 650 F. and maintained there for 5 minutes. The product was ltered to produce a clear uid showing the :following test results:

Table XXV Tin, percent 3.0 CO2, percent 0.01 Neut. No. 10.4

1 1 EXAMPLE XIV 231 g. of the base oil of Example I, 104 g. of the retined oxidized wax distillate of Example I, 38 g. of the sulfonic acid concentrate in 65 g. isoheptane of EX- ample I, 44.6 g. of lead oxide, and 36 ml. of Iwater were charged to a reaction vessel. The stoichiornctric ratios employed were as follows:

Table XXVI Lead oxide 2.0 Oxidate 1.0 Sulfonic acid 0.33

Table XXVII Lead, percent 5.36 Neutl No. 11.1 Sap. No. 31.0

The `foregoing Examples X-XIV are set forth primarily to `demonstrate the use of `other basic inorganic metal compounds in the process of this invention.

EXAMPLE XV 500 g. of a refined wax distillate base oil from a parafiin base crude oil having a gravity of 29 API, Ia Viscosity at 100 F. of 340 SSU, a pour of 0 F. and a V.I. of 93; 62 g. of a powdered barium oxide .and 500 g. of a commercial basic barium sulfonate concentrate were charged to a reaction vessel. The mixture was blown with 1 liter of nitrogen per minute while heating to 600 F. At 350 F. a carboxylic acid containing material consisting of 100 g. of the overhead condensate oil layer produced during the manufacture of the crude oxidate material described in Example II, was added to the mixture. This overhead condensate oil layer mainly comprised an acidic material having a combining weight of about 218 g. calculated from the saponication number of 257. The mass was heated at 600 F. for 2 hours with continued nitrogen blowing and then filtered. The product was tested to give the following results.

Table XX VIII Barium, percent CO2, percent EXAMPLE XVI 138 rg. of the base oil of Example I, 25 g. of the crude wax oxidate described in Example X, 27 g. of the sulfonic acid concentrate of Example I in 46 g. ishoheptane, and 11.2 g. of calcium `oxide were charged to a reaction vessel. The reactants were present in the following stoichiometric amounts:

Table XXIX Calcium oxide 2.0 Oxidate 1.0 Sulfonic acid 0.47

Table XXX Calcium, percent 2.31 CO2, percent 0.72 Basic calcium, percent 11.82

1 By titration with standardized 0.1 normal perchloric acid in glacial acetic acid, using ethyl ether as a sample solvent and titrating to the methyl violet end point.

12 The above Example XVI demonstrates the method of carrying out the process without the separate saponification step.

EXAMPLE XVII A crude oxidate as described in Example I, was filtered to remove insoluble materials. The filtered oxidate had a neutralization number of 82 and a saponiiication number of 141.5, corresponding to a calculated combining weight of 397 grams per saponification equivalent weight.

364 g. of this filtered oxidate, 104 g. of 88 percent formic acid, 168 g. powdered calcium oxide, 54 g. water and 680 g. of an olefin-P2S5 reaction product were combined. This olefin-P2S5 product was prepared in accordance with prior art which has been described in U.S. Patent 2,688,612. This olefin-P2S5 product was a concentrate containing 66 percent by weight of a paraffinic base oil of approximately SSU viscosity of 100 F. The product had a neutralization number of 8.3 and was prepared from a polybutylene olefin having an average molecular weight of about 700.

The resulting reaction mass was heated for one hour at reflux with stirring of the reactor to afford complete neutralization and saponication. It was then blown with nitrogen gas at a rate of 1.0 l./min., heated to 580 F. and maintained at 580 F. for five minutes. A bright and tiuid product was obtained upon filtration, having the following properties:

Table XXXI Ca, percent 2.9 CO2, percent 1.26 Neut. No. (alkaline) 5.7 Viscosity at 100 F., SSU 100 As can be seen by comparison of all the examples, the amounts of the components of a charge of materials to be reacted in accordance with the process of the invention range as shown in the following table:

Table XXXII 1 In excess of the stoiehiometric amount necessary t0 neutralize acidic material present.

2 Weight percent of the stoichiometric quantity oi metal employed.

3 Based on weight of charge materials.

The drawing attached to this specification depicts one method of continuously producing the metal complexcontaining concentrate of this invention.

An anti-foam agent such as a dimethyl siliconekerosene concentrate, a carboxylic acid material such as crude or retined oxidate and/ or formic acid; a dispersant or precursor acid such as a metal sulfonate or sulfonic acid; water; a slurry of metal base in a base oil such as calcium oxide in mineral lubricating oil; additional base oil; and an inert gas such as nitrogen are charged by way of inlet 1 to the mixing reactor Z in which they are thoroughly mixed by the mechanical agitator 3. The

reactor 2 is heated to begin to bring the mixture to the saponication temperature. The mixed mass is continuously pumped by pump 4 to a saponification reactor 5 in which it stirred by agitator 6 and heated to the saponification reaction temperature of about 200 225 F. Volatile components of the reaction mixture are refluxed through condenser 7. The saponified mass is pumped through pump 8 to a solvent stripper 9 heated to a temperature ranging from about 300 to 500 F. and volatile `components are separated for processing or disposal from the reaction mass. From the solvent stripper 9 the fluid mass is continuously pumped by means of pump l2 through heat exchanger 13 and then by means of pump 14 through a hot tube reactor zone 1S which is heated to a temperature range of about 600 to 700 F. The reacted mass is then returned to heat exchanger 13 to be partially cooled and to heat the incoming mass from the solvent stripper by indirect heat exchange. The cooled reacted mass leaves the heat exchanger 13 and passes through cooler 16 and then through a lter system represented by 17. The iinished product is recovered from the lter 17 ready for addition to lubricant compositions.

In the above described system, the component zones can be altered to include a series of reactors or zones to better accomplish a particular step in the process. For example, a number of saponilication reactors can be used in series to ensure complete saponication of the continuously processed mass.

Alternatively, the saponilication reactor can be eliminated and the mass can be solvent stripped and passed immediately through a heat exchanger zone to a hot tube reactor zone wherein saponiiication and thermal decomposition are obtained. The solvent stripper can also be eliminated so that the mass passes directly from the mixing reactor to the hot reaction zone. With this procedure the mixture could be recycled if necessary and then passed through a surge tank before tiltering to accomplish separation of volatiles.

Other modiications can also be used to obtain the product since the basic process is very easily adapted to a continuous process at low equipment investment cost.

Obviously, many modications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope there, and therefore, only such limitations should bc imposed as are indicated in the appended claims.

We claim:

l. A process for preparing a detergent concentrate which comprises heating a saponiable carboxylic acid material selected from the group consisting of aliphatic, cyclo-aliphatic, aromatic, and alkylated aromatic carboxylic acids and their esters, and oxygen-containing derivatives thereof, with an excess of a basic reacting metal compound in the presence of about 1-30 percent of water based on the reaction mixture at a temperature in about the range 12S-250 F., dehydrating the reaction product, and thereafter heating a mixture of the resulting product comprising metal carboxylate and any unreacted basic reacting metal compound, with about 30-90 percent by weight based on the total weight of the mixture of a hydrocarbon lubricating oil and about 1-40 percent by weight based on the total weight of the mixture of a dispersant, at a temperature in the range 40G-850 F. suicient to effect conversion of the said metal carboxylate to metal carbonate, until substantial conversion of the said metal carboxylate to the said metal carbonate has occurred and the said mixture contains 0.1- percent by weight of metal carbonate in stably dispersed form and 0.5-30 percent by weight of the said metal carboxylate, and thereafter cooling the said mixture, said basic reacting metal compound being selected from the group consisting of oxides, hydroxides and carbonates of alkali metals, alkaline earth metals, magnesium, zinc, cadmium, tin, lead and manganese, and said excess thereof being sufficient to give an excess of 20-400 percent by weight of metal in the said mixture over that contained in the neutralized carboxylic acid material and the said dispersant said lubricating oil being substantially stable under the said heating conditions in the range 40G-850 F., and said dispersant being selected from the group consisting of metal sulfonates, metal salts of olefin-phosphorus sulfide reaction products, and metal salts of alkyl phenols and substituted alkyl phenols 2. The process according to claim 1 wherein a substantially inert atmosphere is maintained during the said heating at 40G-850 F.

3. The process according to claim 1 wherein the said mixture is heated at G-850 F. until a stable dispersion is obtained wherein about 19-78 percent of the metal present is in the form of the carbonate.

4. The process according to claim 1 wherein the said carboxylic acid material and the said basic reacting metal compound are heated together in a reaction mixture comprising a minor portion of water.

5. The process according to claim l wherein the said basic reacting metal compound is calcium hydroxide.

6. The process according to claim 1 wherein the said basic reacting metal compound is barium hydroxide.

7. The process according to claim l wherein the said basic reacting metal compound is magnesium hydroxide.

8. The process according to claim l wherein the said dispersant is formed by neutralization of an organic acid material selected from the group consisting of sulfonic acids, olen-phosphorus sulde reaction products, alkyl phenols and sulfurized alkyl phenols in admixture with the said carboxylic acid material, employing an excess of the said basic reacting metal compound over that required to form the normal metal salts with said acid materials equal to about 20-400 percent of that required to form the normal metal salt of the said carboxylic acid material.

9. The process according to claim l wherein the product is nished by blowing with carbon dioxide at about 15C-450 F.

l0. A process for preparing a detergent concentrate which comprises heating a reaction mixture consisting essentially of about 2-20 percent by weight of a carboxylic acid material selected from the group consisting of aliphatic and cyclo-aliphatic hydrocarbon and oxygensubstituted aliphatic and cyclo-aliphatic hydrocarbon carboxylic acids and their esters, about 50-75 percent by weight of a hydrocarbon lubricating oil, about 1-30 percent by weight of water and an excess of a basic reacting metal compound, said heating being carried out at a temperature in about the range 12S-250 F. until neutralization and saponication reactions are substantially complete, dehydrating the reaction mixture thereafter further heating the said reaction mixture containing about l-4O percent by weight of a dispersant at a temperature in the range 60G-850 F. in an inert atmosphere until a stable dispersion is obtained wherein about 19-78 percent of the metal present is in the form of the carbonate, and thereafter cooling the resulting product, said dispersant being an oil-soluble metal salt of an organic acid selected from the group consisting of sulfonic acids, olefin-phosphorus sulfide reaction products and alkyl and substituted alkyl phenols, said basic reacting metal compound being selected from the group consisting of oxides and hydroxides of alkali metals, alkaline earth metals, magnesium, zinc, cadmium, tin, lead and manganese, and said excess thereof being suicient to give an excess of 20-400 percent of metal in the said mixture over that contained in the neutralized carboxylic acid material and in the dispersant.

1l. The process according to claim l0 wherein the said dispersant is formed by neutralization of the said organic acid in admixture with the said carboxylic acid material, employing an excess of the said basic reacting metal compound over that required to form the normal metal salts of said acids equal to about 50-200 percent of that required to form the normal metal salt of the said carboxylic acid material.

12. A process for preparing a detergent concentrate which comprises providing a mixture consisting essentially of about 30-90 percent by Weight of a hydrocarbon lubricating oil, about 1-40 percent by weight of a dispersant chosen from the class consisting of metal sulfonates, metal salts of olefin-phosphorus sulde reaction products and metal salts of alkyl phenols and substituted alkyl phenols, a metal carboxylate chosen from the class consisting of metal salts of aliphatic, cyclo-aliphatic, aromatic and alkylated aromatic carboxylic acids and oxygen-containing derivatives thereof in an amount sucient to provide about 5-50 percent by Weight of the carboxylate component in the said mixture, and a basic metal compound selected from the class consisting of metal oxides, hydroxides and carbonates in an amount sufcient to provide additional metal in the said mixture equal to about 20-400 percent by Weight of the metal contained in the said metal carboxylate and in said dispersant, heating the said mixture in the range 40G-850 F. for at least about 1 minute and for a sufficient time to provide 0.1-15 percent by Weight of stably dispersed metal base in the reaction mixture, and thereafter cooling the said reaction mixture and separating any undispersed basic metal compound, said dispersant, said metal carboxylate and said basic metal compound having their metal component selected from the group consisting of alkali metals, alkaline earth metals, magnesium, zinc, cadmium, tin, lead and manganese.

16 13. The process according to claim 12 wherein a substantially inert atmosphere is maintained during the said heating at 400-850 F.

References Cited in the le of this patent UNITED STATES PATENTS 2,417,428 McLennan Mar. 18, 1947 2,417,433 McLennan Mar. 18, 1947 2,739,124 Otto et al Mar. 20, 1956 2,739,125 Myers et al Mar. 20, 1956 2,763,615 Faust Sept. 18, 1956 2,779,784 Sharrah Jan. 29, 1957 2,902,511 Culmer Sept. l, 1959 2,929,785 Morway et al. Mar. 22, 1960 

1. A PROCESS FOR PREPARING A DETERGENT CONCENTRATE WHICH COMPRISES HEATING A SAPONIFIABLE CARBOXYLIC ACID MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC, CYCLO-ALIPHATIC, AROMATIC, AND ALKYLATED AROMATIC CARBOXYLIC ACIDS AND THEIR ESTERS, AND OXYGEN-CONTAINING DERIVATIVES THEREOF, WITH AN EXCESS OF A BASIC REACTING METAL COMPOUND IN THE PRESENCE OF ABOUT 1-30 PERCENT OF WATER BASED ON THE REACTION MIXTURE AT A TEMPERATURE IN ABOUT THE RANGE 125-250* F, DEHYDRATING THE REACTION PRODUCT, AND THEREAFTER HEATING A MIXTURE OF THE RESULTING PRODUCT COMPRISING METAL CARBOXYLATE AND ANY UNREACTED BASIC REACTING METAL COMPOUND, WITH ABOUT 30-90 PERCENT BY WEIGHT BASED ON THE TOTAL WEIGHT OF THE MIXTURE OF A HYDROCARBON LUBRICATING OIL AND ABOUT 1-40 PERCENT BY WEIGHT BASED ON THE TOTAL WEIGHT OF THE MIXTURE OF A DISPERSANT, AT A TEMPERATURE IN THE RANGE 400-850* F, SUFFICIENT TO EFFECT CONVERSION OF THE SAID METAL CARBOXYLATE TO METAL CARBONATE, UNTIL SUBSTANTIAL CONVERSION OF THE SAID METAL CARBOXYLATE TO THE SAID METAL CARBONATE HAS OCCURED AND THE SAID MIXTURE CONTAINS 0.1-15 PERCENT BY WEIGHT OF METAL CARBONATE IN STABLY DISPERSED FORM AND 0.5-30 PERCENT BY WEIGHT OF THE SAID METAL CARBOXYLATE, AND THEREAFTER COOLING THE SAID MIXTURE, SAID BASIC REACTING METAL COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF OXIDES, HYDROXIDES AND CARBONATES OF ALKALI METALS, ALKALINE EARTH METALS, MAGNESIUM, ZINC, CADMIUM, TIN LEAD AND MANGANESE, AND SAID EXCESS THEREOF BEING SUFFICIENT TO GIVE AN EXCESS OF 20-400 PERCENT BY WEIGHT OF METAL IN THE SAID MIXTURE OVER THAT CONTAINED IN THE NEUTRALIZED CARBOXYLIC ACID MATERIAL AND THE SAID DISPERSANT SAID LUBRICATING OIL BEING SUBSTANTIALLY STABLE UNDER THE SAID HEATING CONDITIONS IN THE RANGE 400-850* F., AND SAID DISPERSANT BEING SELECTED FROM THE GROUP CONSISTING OF METAL SULFONATES, METAL SALTS OF OLEFIN-PHOSPHORUS SULFIDE REACTION PRODUCTS, AND METAL SALTS OF ALKYL PHENOLS AND SUBSTITUTED ALKYL PHENOLS. 